Multi-layered article

Abstract

The present invention relates to a multi-layered article comprising a metal part and a coating, having outstanding adhesion between said coating and said metal part, even in severe environment conditions, such as marine environment, high pressure and high temperature.

1 . A multi-layered article comprising:
 a metal part having at least one surface (S);   a first layer (L 1 ) having a first surface (S 1 -L 1 ) directly adhered to said surface (S) and a second surface (S 2 -L 1 ), said layer (L 1 ) being made from a first composition (C 1 ), said composition (C 1 ) comprising at least one epoxy resin (E 1 );   a second layer (L 2 ) having a first surface (S 1 -L 2 ) directly adhered to said second surface (S 2 -L 1 ) of said layer (L 1 ) and a second surface (S 2 -L 2 ), said layer (L 2 ) being made from a second composition (C 2 ), said composition (C 2 ) comprising at least one epoxy resin (E 2 ) and at least one melt-processable perfluoropolymer [polymer (P a )]   and   optionally, a third layer (L 3 ) having a first surface (S 1 -L 3 ) directly adhered to said second surface (S 2 -L 2 ) of said layer (L 2 ), and a second surface (S 2 -L 3 ), said layer (L 3 ) being made from a third composition (C 3 ), said composition (C 3 ) comprising at least one melt-processable perfluoropolymer.   
     
     
         2 . The multi-layered article according to  claim 1 , wherein said resin (E 1 ) and/or said resin (E 2 ) are prepared by the condensation of epoxy compounds with polyhydric-organic compounds. 
     
     
         3 . The multi-layered article according to  claim 1 , wherein said polymer (P a ) and said polymer (P b ), identical or different each other, are a polymer comprising recurring units derived from at least one perfluorinated monomer. 
     
     
         4 . The multi-layered article according to  claim 3 , wherein said at least one perfluorinated monomer is selected from the group comprising:
 C 2 -C 8  perfluoroolefins;   chloro- and/or bromo- and/or iodo-C 2 -C 6  fluoroolefins;   CF 2 ═CFOR f1 , wherein R f1  is a C 1 -C 6  perfluoroalkyl group, or a group of formula —CFOCF 2 OR f2  wherein R f2  is a C 1 -C 6  perfluoroalkyl group, a cyclic C 5 -C 6  perfluoroalkyl group, or a C 1 -C 12  (per)fluorooxyalkyl group comprising one or more ether groups;   perfluorodioxoles of formula:   
       
         
           
           
               
               
           
         
       
       wherein each of R f3 , R f4 , R f5 , R f6 , equal of different each other, is independently a fluorine atom, a C 1 -C 6  perfluoroalkyl group, optionally comprising one or more oxygen atom. 
     
     
         5 . The multi-layered article according to  claim 1 , wherein said composition (C 1 ) comprises at least one resin (E 1 ) and optionally further ingredients. 
     
     
         6 . The multi-layered article according to  claim 1 , wherein composition (C 2 ) comprises at least one resin (E 2 ), at least one polymer (P a ), optionally at least one oxide of cobalt and optionally further ingredients. 
     
     
         7 . The multi-layered article according to  claim 1 , wherein said polymer (P a ) comprises one or molar polar functional groups [polymer (P a -F)]. 
     
     
         8 . The multi-layered article according to  claim 7 , wherein said one or more polar functional groups are selected from the group consisting of carboxylic groups in acid, acid halide or salt form; sulfonic groups in acid, acid halide or salt form; epoxide groups; silyl groups, alkoxysilane groups; hydroxyl groups; and isocyanate groups. 
     
     
         9 . The multi-layered article according to  claim 5 , wherein said composition (C 1 ) comprises said at least one resin (E 1 ) in an amount of from 5 to 45 wt. % based on the total weight of composition (C 1 ). 
     
     
         10 . The multi-layered article according to  claim 6 , wherein said composition (C 2 ) comprises at least one resin (E 2 ) in an amount of from 0.01 to 20.25 wt. % based on the total weight of composition (C 2 ). 
     
     
         11 . The multi-layered article according to  claim 6 , wherein said composition (C 2 ) comprises polymer (P a ) in an amount of from 55 to 99.99 wt. % based on the total weight of composition (C 2 ). 
     
     
         12 . The multi-layered article according to  claim 6 , wherein said composition (C 2 ) comprises said oxide of cobalt in an amount of from 0.05 to 10 wt. % based on the total weight of composition (C 2 ). 
     
     
         13 . The multi-layered article according to  claim 1 , wherein said composition (C 3 ) comprises at least one melt-processable perfluoropolymer [polymer (P b )], and optionally further ingredients. 
     
     
         14 . The multi-layered article according to  claim 13 , wherein said composition (C 3 ) comprises polymer (P b ) in an amount of from 50 to 100 wt. % based on the total weight of composition (C 3 ). 
     
     
         15 . A method comprising the following steps:
 applying a first composition (C 1 ), said composition (C 1 ) comprising at least one epoxy resin [resin (E 1 )], to an article comprising a metal part, said metal part having at least one surface (S) so as to provide a layer (L 1 ) having a first surface (S 1 -L 1 ) directly adhered to said surface (S), and a second surface (S 2 -L 1 );   applying a second composition (C 2 ), said composition (C 2 ) comprising at least one at least one epoxy resin (E 2 ) and at least one melt-processable perfluoropolymer [polymer (P a )], to the article so as to provide a layer (L 2 ) having a first surface (S 1 -L 2 ) directly adhered to said second surface (S 2 -L 1 ), and a second surface (S 2 -L 2 ); and   optionally, applying a third composition (C 3 ), said composition (C 3 ) comprising at least one perfluoropolymer [polymer (P b )], to the article so as to provide a layer (L 3 ) having a first surface (S 1 -L 3 ) directly adhered to said second surface (S 2 -L 2 ), and a second surface (S 2 -L 3 ).   
     
     
         16 . The method according to  claim 15 , further comprising applying a fourth composition (C 4 ), said composition (C 4 ) comprising at least one perfluoropolymer [polymer (P c )] and optionally further ingredients, to the article so as to provide a layer (L 4 ) having a first surface (S 1 -L 4 ) directly adhered to said second surface (S 2 -L 3 ) of said layer (L 3 ). 
     
     
         17 . The multi-layered article according to  claim 2 , wherein the epoxy compounds are selected from epichlorohydrin and glycerol dichlorohydrin and wherein the polyhydric-organic compounds are selected from alcohols, dihydric alcohols, dihydric phenols and trihydric phenols. 
     
     
         18 . The multi-layered article according to  claim 1 , wherein
 composition (C 1 ) comprises said at least one resin (E 1 ) in an amount of from 5 to 45 wt. % based on the total weight of composition (C 1 );   composition (C 2 ) comprises
 at least one resin (E 2 ) in an amount of from 0.01 to 20.25 wt. %, 
 polymer (P a ) in an amount of from 55 to 99.99 wt. %, and 
 an oxide of cobalt in an amount of from 0.05 to 10 wt. %, 
 each of the above based on the total weight of composition (C 2 ); 
   composition (C 3 ) comprises polymer (P b ) in an amount of from 50 to 100 wt. % based on the total weight of composition (C 3 );   resin (E 1 ) and/or resin (E 2 ) are each independently prepared by the condensation of at least one epoxy compound selected from epichlorohydrin and glycerol dichlorohydrin with at least one polyhydric-organic compound selected from alcohols; dihydric alcohols; dihydric phenols; and trihydric phenols;   polymer (P a ) and polymer (P b ), identical or different each other, are a polymer comprising recurring units derived from at least one perfluorinated monomer selected from:
 C 2 -C 8  perfluoroolefins; 
 chloro- and/or bromo- and/or iodo-C 2 -C 6  fluoroolefins; 
 CF 2 ═CFOR f1 , wherein R f1  is a C 1 -C 6  perfluoroalkyl group, or a group of formula —CFOCF 2 OR f2  wherein R f2  is a C 1 -C 6  perfluoroalkyl group, a cyclic C 5 -C 6  perfluoroalkyl group, or a C 1 -C 12  (per)fluorooxyalkyl group comprising one or more ether groups; 
 perfluorodioxoles of formula: 
   
       
         
           
           
               
               
           
         
       
       wherein each of R f3 , R f4 , R f5 , R f6 , equal of different each other, is independently a fluorine atom, a C 1 -C 6  perfluoroalkyl group, optionally comprising one or more oxygen atom; and
 polymer (P a ) comprises one or molar polar functional groups, each independently selected from the group consisting of carboxylic groups in acid, acid halide or salt form; sulfonic groups in acid, acid halide or salt form; epoxide groups; silyl groups, alkoxysilane groups; hydroxyl groups; and isocyanate groups.